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  • C08K5/15—Heterocyclic compounds having oxygen in the ring
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  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0853—Vinylacetate
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
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  • C08L25/06—Polystyrene
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  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
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  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the present invention relates to a plasticizer composition, a resin composition and methods for preparing the plasticizer thereof.
• plasticizers In common plasticizers, alcohols react with polycarboxylic acids such as phthalic acid and adipic acid to prepare esters corresponding thereto.
• polycarboxylic acids such as phthalic acid and adipic acid
• plasticizer compositions capable of replacing phthalate-based plasticizers such as terephthalate-based, adipate-based and other polymer-based have been continued considering domestic and overseas restrictions on phthalate-based plasticizers harmful to the human body.
• plasticizers need to be used considering discoloration, a migration property, processibility and the like.
• a plasticizer, a filler, a stabilizer, a viscosity depressant, a dispersant, an antifoaming agent, a foaming agent and the like are mixed to a PVC resin depending on tensile strength, an elongation rate, light resistance, a migration property, a gelling property, processibility or the like, properties required for each industry in such various applications.
• an object of the present invention is to provide a plasticizer capable of improving physical properties such as plasticizing efficiency, a migration property and a gelling property required in formularization of sheets and the like when used as a plasticizer of a resin composition, a method for preparing the same, and a resin composition comprising the same.
• One embodiment of the present invention provides a plasticizer composition comprising a mixture of terephthalate-based material; and epoxidized oil, wherein weight ratio of the terephthalate-based material and the epoxidized oil is from 99:1 to 1:99.
• the weight ratio of the terephthalate-based material and the epoxidized oil may be from 95:5 to 50:50.
• the weight ratio of the terephthalate-based material and the epoxidized oil may be from 95:5 to 60:40.
• the mixture of the terephthalate-based material may be a first mixture mixing di(2-ethylhexyl) terephthalate, butyl(2-ethylhexyl) terephthalate and dibutyl terephthalate, a second mixture mixing diisononyl terephthalate, butylisononyl terephthalate and dibutyl terephthalate, or a third mixture mixing di(2-ethylhexyl) terephthalate, (2-ethylhexyl)isononyl terephthalate and diisononyl terephthalate.
• the first mixture may comprise the di(2-3.0 mol % to 99.0 mol % of ethylhexyl) terephthalate; 0.5 mol % to 96.5 mol % of the butyl(2-ethylhexyl) terephthalate; and 0.5 mol % to 96.5 mol % of the dibutyl terephthalate.
• the second mixture may comprise 3.0 mol % to 99.0 mol % of the diisononyl terephthalate; 0.5 mol % to 96.5 mol % of the butylisononyl terephthalate; and 0.5 mol % to 96.5 mol % of the dibutyl terephthalate.
• the third mixture may comprise 3.0 mol % to 99.0 mol % of the di(2-ethylhexyl) terephthalate in; 0.5 mol % to 96.5 mol % of the (2-ethylhexyl)isononyl terephthalate in; and 0.5 mol % to 96.5 mol % of the diisononyl terephthalate.
• the epoxidized oil may comprise at least one selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil and epoxidized linoleate.
• the plasticizer composition may further comprise an additive, and the additive may comprise an acetyl citrate-based material, a trimellitate-based material or a mixture thereof.
• the additive may be included in an amount of 1 part by weight to 100 parts by weight based on 100 parts by weight of the plasticizer composition.
• the acetyl citrate-based material may comprise at least one selected from the group consisting of a hybrid C4-C9 alkyl substituted acetyl citrate and a non-hybrid C4-C9 alkyl substituted acetyl citrate.
• the trimellitate-based material may comprise at least one selected from the group consisting of tributyltrimellitate (TBTM), triisononyltrimellitate (TINTM) and tri(2-ethylhexyl)trimellitate (TOTM or TEHTM).
• TBTM tributyltrimellitate
• TINTM triisononyltrimellitate
• TOTM or TEHTM tri(2-ethylhexyl)trimellitate
• Another embodiment of the present invention provides a method for preparing a plasticizer composition, the method comprises providing a terephthalate-based material and epoxidized oil; and blending the terephthalate-based material and the epoxidized oil at weight ratio of 99:1 to 1:99 to prepare a plasticizer composition, wherein the terephthalate-based material is a mixture.
• the terephthalate-based material may be prepared by conducting direct esterification of an alcohol and a terephthalic acid, wherein the alcohol is at least one selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol; or conducting trans esterification of a terephthalate and an alcohol, wherein the terephthalate is any one selected from among di(2-ethylhexyl) terephthalate or diisononyl terephthalate, and the alcohol is any one selected from among butyl alcohol or isobutyl alcohol.
• the method may further comprise mixing 1 part by weight to 100 parts by weight of an additive based on 100 parts by weight of the plasticizer composition.
• Still another embodiment of the present invention provides a resin composition comprising 100 parts by weight of a resin; and 5 parts by weight to 150 parts by weight of the plasticizer composition of claim 1 .
• the resin may be at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomers.
• the resin composition may be material for at least one selected from the group consisting of wires, flooring materials, automotive interior materials, films, sheets, wallpapers and tubes.
• a plasticizer composition according to one embodiment of the present invention is capable of providing excellent properties such as migration resistance and volatility resistance as well as excellent plasticizing efficiency, tensile strength and elongation rate when used in a resin composition.
• an ester-based placitisizer composition comprising dibutyl terephthalate (DBTP), butylisononyl terephthalate (BINTP) and diisononyl terephthalate (DINTP) in ranges of 4.0% by weight, 35.0% by weight and 61.0% by weight, respectively.
• DBTP dibutyl terephthalate
• BINTP butylisononyl terephthalate
• DINTP diisononyl terephthalate
• the reaction product was conducted mixed distillation to remove butanol and 2-ethylhexyl alcohol, and a first mixture was finally prepared.
• extractive distillation was conducted for 0.5 hours to 4 hours under reduced pressure in order to remove unreacted raw materials.
• Steam distillation was conducted for 0.5 hours to 3 hours under reduced pressure using steam in order to remove unreacted raw materials to a specific content level or lower, and neutralization was conducted using an alkali solution after cooling the reaction solution to approximately 90° C. Water washing may be additionally conducted and then the reaction solution was dehydrated to remove moisture.
• a filter medium was added to the moisture-removed reaction solution, and the result was stirred for a certain period of time and then filtered to finally prepare a third mixture.
• Plasticizer compositions of Examples 1 to 4 were prepared using the materials prepared in Preparation Examples 1 to 9 and epoxidized oil, and the preparations are summarized in the following Tables 1 to 6. Physical property evaluations on the plasticizer compositions were conducted according to the following test items.
• Measurement conditions for the following test items may be for illustrative purposes for describing measurement methods, and specific measurement and evaluation conditions for the test examples using other conditions may be referred to in each of the test examples.
• Elongation rate (%) [length after elongation/initial length] ⁇ 100.
• Measurement on tensile and elongation retention measures tensile and elongation rate properties remaining on the specimen after applying heat for a certain period of time at a specific temperature, and the methods of measurement are the same as the methods measuring the tensile strength and the elongation rate.
• a specimen having a thickness of 2 mm or greater was prepared in accordance with the KSM-3156, and a load of 1 kgf/cm 2 was applied after attaching PS plates on both surfaces of the specimen.
• the specimen was left unattended for 72 hours in a forced convection oven (80° C.) and then taken out and cooled for 4 hours at room temperature. After that, the PS plates attached on both surfaces of the specimen were removed, weights before and after leaving the specimen unattended in the oven were measured, and the amount of migration loss was calculated through the equation such as below.
• Amount of migration loss (%) [(initial weight of specimen at room temperature-weight of specimen after being left unattended in oven)/initial weight of specimen at room temperature] ⁇ 100
• Volatile loss (%) [(initial specimen weight-specimen weight after working)/initial specimen weight] ⁇ 100.
• the specimen was left unattended for a certain period of time as being bent, and the degree of migration (the degree of oozing) was observed and expressed as a number.
• the number being closer to 0 represents excellent properties.
• the specimen was held in QUV and UV irradiated for 200 hours in accordance with the method of ASTM 4329-13, and then a change in the color was calculated using a reflectometer.
• the degree of discoloration in the initial specimen and the specimen after the volatile loss test using the volatile loss measuring method was measured.
• the measurement value was determined by the changed values in an E value with respect to L,a and b values using a colorimeter.
• the specimens were prepared by, referring to the ASTM D638, mixing 50 parts by weight of the mixed plasticizer composition and 3 parts by weight of a stabilizer (BZ153T) to 100 parts by weight of PVC in a 3 L super mixer under 98° C. and 700 rpm, then making a 5 mm sheet by working on the result for 4 minutes at 160° C. using a roll mill, and then making a 1 mm to 3 mm sheet after pressing the result for 2.5 minutes at a low pressure and 2 minutes at a high pressure at 180° C.
• Physical properties were evaluated as each of the evaluation items described above using each specimen, and the results are summarized in the following Table 4.
• the plasticizer composition prepared by mixing a terephthalate-based material and epoxidized oil, the plasticizer composition was capable of enhancing resistance for migration loss or stress while having an equal or higher level of basic physical properties of a plasticizer, resulted in more improved hardness and an elongation rate, and was capable of enhancing processibility through a higher absorption rate.
• plasticizer composition of Examples 2-1 to 2-5 prepared by mixing epoxidized oil and the first mixture (a terephthalate-based material) exhibited an equal or higher level in the physical properties such as tensile strength, volatile loss, migration loss and an elongation rate compared to the existing DOTP plasticizer of Comparative Example 1.
• the plasticizer composition was capable of enhancing migration loss or resistance for stress while having an equal or higher level of basic physical properties of a plasticizer, still maintained properties in high-temperature environments due to particularly improved volatile loss, and in addition to these, resulted in more improved hardness and an elongation rate, and was capable of enhancing processibility through a higher absorption rate.
• the specimens were prepared by, referring to the ASTM D638, mixing 50 parts by weight of the mixed plasticizer composition, 40 parts by weight of a filler (OMYA1T), 5 parts by weight of a stabilizer (RUP-144) and 0.3 parts by weight of a lubricant (St-A) to 100 parts by weight of PVC in a 3 L super mixer under 98° C. and 700 rpm, making a compound by working on the result for 4 minutes at 160° C. using a roll mill, and then pressing the result for 2.5 minutes at a low pressure and 2 minutes at a high pressure at 180° C.
• Physical properties were evaluated as each of the evaluation items described above using each specimen, and the results are summarized in the following Table 6.
• the plasticizer composition of Examples 3-1 to 3-6 were prepared by mixing epoxidized oil and DOP (a terephthalate-based material) and further adding TOTM and TBTM among trimellitate-based materials, acetyl trialkyl citrate and the like as the additive. It was identified that the plasticizer composition of Examples 3-1 to 3-6 exhibited an equal or higher level in the physical properties such as tensile strength, volatile loss, migration loss and an elongation rate compared to the existing DIDP plasticizer of Comparative Example 2. In the case of the volatile loss, ATBC and TBTM having a relatively small molecular weight exhibited similar values compared to Comparative Example 2. This indicates that an overall physical property level may be adjusted to the equal or higher physical property level compared to DIDP through effective adjustment in the product composition ratio, and securing more superior products not only in product physical properties but also in economic feasibility becomes possible therethrough.
• the present invention has technological features in providing a plasticizer composition capable of improving poor physical properties having been caused by structural limitation.
• a plasticizer composition comprising a terephthalate-based material
• the terephthalate-based material may be included in an amount selected from a range of from 1 wt % to 99 wt %, from 20 wt % to 99 wt %, from 40 wt % to 99 wt %, from 50 wt % to 95 wt %, from 60 wt % to 90 wt %, or the like, based on the total weight of the composition.
• the terephthalate-based material may have a terminal group independently selected from the group consisting of C1-C12 alkyl groups, C3-C11 alkyl groups, C4-C10 alkyl groups, C8-C10 alkyl groups, C8-C9 alkyl groups or C8 alkyl group.
• the terephthalate-based material may be a mixture of three kinds of terephthalate-based materials are mixed, and for example, may be a first mixture mixing di(2-ethylhexyl) terephthalate, butyl(2-ethylhexyl) terephthalate and dibutyl terephthalate, a second mixture mixing diisononyl terephthalate, butylisononyl terephthalate and dibutyl terephthalate, and a third mixture mixing di(2-ethylhexyl) terephthalate, (2-ethylhexyl)isononyl terephthalate and diisononyl terephthalate.
• the first mixture to the third mixture may have specific composition ratios, and the first mixture may have 3.0 mol % to 99.0 mol % of the di(2-ethylhexyl) terephthalate, 0.5 mol % to 96.5 mol % of the butyl(2-ethylhexyl) terephthalate and 0.5 mol % to 96.5 mol % of the dibutyl terephthalate; the second mixture may have 3.0 mol % to 99.0 mol % of the diisononyl terephthalate, 0.5 mol % to 96.5 mol % of the butylisononyl terephthalate and 0.5 mol % to 96.5 mol % of the dibutyl terephthalaten; and the third mixture may have 3.0 mol % to 99.0 mol % of the di(2-ethylhexyl) terephthalate, 0.5 mol % to 96.5 % of
• the composition ratio may be a mixing composition ratio produced by an esterification, or an intended composition ratio by additionally adding specific compounds, and the mixing composition ratio may be properly adjusted to be suitable for target physical properties.
• the plasticizer composition may further comprise epoxidized oil
• the epoxidized oil may comprise epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil, epoxidized linoleate or mixtures thereof.
• weight ratio of the terephthalate-based material and the epoxidized oil may be from 99:1 to 1:99.
• the weight ratio of the terephthalate-based material and the epoxidized oil may be from 99:1 to 20:80, from 99:1 to 40:60, from 99:1 to 50:50 or from 99:1 to 60:40.
• weight ratio of the terephthalate-based material and the epoxidized oil may be from 95:5 to 50:50 or from 90:10 to 60:40.
• a migration resistance property for stress may become excellent. Physical properties such as tensile strength or an elongation rate may somewhat decline, but may be included in the required physical property range. Accordingly, required physical properties may be freely controlled by the epoxidized oil content adjustment, and the epoxidized oil may be properly used depending on the use of a vinyl chloride-based resin composition.
• the epoxidized oil may be preferably included in approximately 10 wt % or greater and more preferably included in 20 wt % or greater with respect to the total amount of the plasticizer composition.
• epoxidized oil is sometimes included as a stabilizing agent when preparing a plasticizer, however, this may be distinguished from the above-mentioned epoxidized oil used as a second plasticizer.
• Using the terephthalate-based material as a first plasticizer is more environmental-friendly compared to phthalate-based materials such as diisodecyl phthalate having been used in the art as a plasticizer, however, reaching a level suited for commercialization may be difficult in terms of economic feasibility or existing physical properties, and adding epoxidized oil at a level of a stabilizing agent may be difficult to come close to physical properties prepared by existing plasticizers.
• the plasticizer composition comprises a terephthalate-based material and epoxidized oil, and may further comprise an additive.
• the additive may be included in 1 part by weight to 100 parts by weight and preferably in 1 part by weight to 80 parts by weight based on 100 parts by weight of the plasticizer composition.
• the additive may be mixed with the terephthalate-based compound alone and enhance a stress property and the like of a resin composition, however, even when such a small amount of the additive is mixed and included in the plasticizer composition, a compound and the like having excellent physical properties may be prepared.
• a larger quantity of the additive is included, physical properties of the plasticizer composition may be out of control in controlling physical properties suitable for application, and problems such as excessively improving undesirable physical properties or declining desirable physical properties may occur.
• the content of the terephthalate-based material is relatively low.
• physical properties such as plasticizing efficiency relating to processibility may not be relatively superior among various physical properties. And such a property may be complemented by further adding the additive.
• a trimellitate-based material or a mixture thereof as the additive, empty space may be largely formed in the plasticizer composition due to large steric hindrance of the materials, and consequently, effects such as processibility enhancement may be additionally accomplished and preferably, adding materials having a smaller molecular weight among the additives may be more helpful in enhancing processibility.
• the acetyl citrate-based material may comprise at least one selected from the group consisting of a hybrid C4-C9 alkyl substituted acetyl citrate-based materials and a non-hybrid C4-C9 alkyl substituted acetyl citrate-based materials.
• the hybrid C4-C9 alkyl substituted acetyl citrate-based materials may be citrate having a combined substituent of C4-C8 alkyl groups such as 1,2-dibutyl 3-(2-ethylhexyl) 2-acetylpropane-1,2,3-tricarboxylate, 1,3-dibutyl 2-(2-ethylhexyl) 2-acetylpropane-1,2,3-tricarboxylate, 1-butyl 2,3-bis(2-ethylhexyl) 2-acetylpropane-1,2,3-tricarboxylate or 2-butyl 1,3-bis(2-ethylhexyl) 2-acetylpropane-1,2,3-tricarboxylate; acetyl citrate having a combined substituent of C5-C7 alkyl groups such as 1,2-dipentyl 3-heptyl 2-acetylpropane-1,2,3-tricarboxylate,
• hybrid C4-C9 alkyl substituted acetyl citrate-based materials may be acetyl citrate having a combined substituent of two alkyl groups having a different number of carbon atoms selected from 4 to 9, and the like.
• the alkyl group may be linear or branched.
• the C4-C9 alkyl group may be linear or branched.
• the non-hybrid C4-C9 alkyl substituted acetyl citrate-based materials may comprise tributyl acetyl citrate (ATBC), tripentyl acetyl citrate (ATPC), trihexyl acetyl citrate (ATHC), triheptyl acetyl citrate (ATHC), trioctyl acetyl citrate (ATOC), trinonyl acetyl citrate (ATNC) or the like
• the butyl group to the nonyl group may comprise each structural isomer, for example, an isobutyl group in the case of the butyl group, and a 2-ethylhexyl group in the case of the octyl group.
• non-hybrid C4-C9 alkyl substituted acetyl citrate may be preferable compared to hybrid alkyl substituted acetyl citrate, and tri(2-ethylhexyl) acetyl citrate may be used little more frequently.
• the use of the plasticizer may vary depending on the molecular weight, and when the material having a large molecular weight is used, physical properties of the plasticizer oozing out such as migration loss or volatile loss may be complemented, and accordingly, the use in compound industries and the like may be preferable, and in the case of the material having a small molecular weight, the use in the fields requiring excellent processibility may be preferable.
• the trimellitate-based material may comprise a non-hybrid C4-C9 alkyl trimellitate-based material, and the C4-C9 alkyl group may be linear or branched.
• the trimellitate-based material may be tributyl trimellitate (TBTM), triisobutyl trimellitate (TiBTM), triethylhexyl trimellitate (TEHTM), triisononyl trimellitate (TINTM) or the like.
• a blending method may be used, and one example of the blending preparation method is as follows.
• the plasticizer composition may be prepared by providing a terephthalate-based material and epoxidized oil, and blending the terephthalate-based material and the epoxidized oil at weight ratio of from 1:99 to 99:1, and the terephthalate-based material is a mixture.
• the terephthalate-based material is a mixture of three kinds of terephthalate compounds, and may be prepared by preparing the terephthalate compounds through the direct esterification and mixing the result.
• the terephthalate compounds may be prepared by conducting the direct esterification of an alcohol and terephthalic acid, and the alcohol is at least one selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol.
• the direct esterification reaction may be conducted by adding terephthalic acid to an alcohol, then adding a catalyst, and reacting the result under nitrogen atmosphere; removing the unreacted alcohol, and neutralizing the unreacted acid; and dehydrating and filtering through vacuum distillation.
• the alcohol used in the blending preparation method may be used 150 mol % to 500 mol %, 200 mol % to 400 mol %, 200 mol % to 350 mol %, 250 mol % to 400 mol % or 270 mol % to 330 mol % based on 100 mol % of the terephthalic acid.
• the alcohol used in the blending preparation method may be used 150 mol % to 500 mol %, 200 mol % to 400 mol %, 200 mol % to 350 mol %, 250 mol % to 400 mol % or 270 mol % to 330 mol % based on 100 mol % of the terephthalic acid.
• the catalyst used in the blending preparation method may comprise at least one selected from the group consisting of acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfuric acid, metal salts such as aluminum sulfate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate, metal oxides such as heteropolyacid, natural/synthetic zeolite, cation and anion exchange resins, and organic metals such as tetra alkyl titanate and polymers thereof. As specific examples thereof, tetra alkyl titanate may be used as the catalyst.
• acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methan
• the amount of the catalyst used may be different depending on the types, and as one example, a homogeneous catalyst may be used in an amount of 0.01 wt % to 5 wt %, 0.01 wt % to 3 wt %, 1 wt % to 5 wt % or 2 wt % to 4 wt % based on 100 wt % of the total reactants, and a heterogeneous catalyst may be used in an amount of 5 wt % to 200 wt %, 5 wt % to 100 wt %, 20 wt % to 200 wt % or 20 wt % to 150 wt % based on the total weight of the reactants.
• reaction temperature may be from 180° C. to 280° C., from 200° C. to 250° C. or from 210° C. to 230° C.
• the terephthalate-based material is a mixture of three kinds of terephthalate compounds, and the terephthalate compounds may be prepared by conducting a transesterification of terephthalate compound and an alcohol, the terephthalate compound is any one selected from the group consisting of di(2-ethylhexyl) terephthalate and diisononyl terephthalate, and the alcohol is selected from any one the group consisting of butyl alcohol and isobutyl alcohol.
• trans-esterification used in the present invention means a reaction in which an alcohol and an ester to exchange R′′ of the ester with R′ of the alcohol as shown in Reaction Formula 1 below:
• 3 kinds of ester compositions may be produced by three number of cases such as alkoxide of the alcohol attacking carbon of two ester (RCOOR′′) groups present in the ester-based compound; alkoxide of the alcohol attacking carbon of one ester (RCOOR′′) group present in the ester-based compound; and being unreacted with no reactions.
• the trans-esterification has an advantage of not causing a problem of waste water compared to an esterification reaction between acid-alcohol, and may be progressed without a catalyst, and therefore, is capable of solving a problem caused by the use of an acid catalyst.
• di(2-ethylhexyl) terephthalate and butyl alcohol may produce a mixture of di(2-ethylhexyl) terephthalate, butyl(2-ethylhexyl) terephthalate and dibutyl terephthalate through the trans-esterification, and the three kinds of terephthalate may be formed in amounts of 3.0 wt % to 70 wt % of di(2-ethylhexyl) terephthalate, 0.5 wt % to 50 wt % of butyl(2-ethylhexyl) terephthalate, and 0.5 wt % to 85 wt % of dibutyl terephthalate, respectively, and specifically, 10 wt % to 50 wt % of di(2-ethylhexyl) terephthalate, 0.5 wt % to 50 wt % of butyl(2-eth)
• the mixture prepared by the trans-esterification may control a composition ratio of the mixture depending on the amount of the alcohol added.
• the amount of the alcohol added may be 0.1 parts by weight to 89.9 parts by weight, specifically 3 parts by weight to 50 parts by weight and more specifically 5 parts by weight to 40 parts by weight based on 100 parts by weight of the terephthalate compound.
• a mole fraction of the terephthalate compound participating in the trans-esterification increases as the amount of the added alcohol increases, and therefore, content of the two terephthalate compounds, a product, may increase in the mixture, and accordingly, the content of the terephthalate compound present unreacted corresponding thereto tends to decrease.
• a molar ratio of the terephthalate compound and the alcohol, which are reactants may be, for example, from 1:0.005 to 5.0, from 1:0.05 to 2.5, or from 1:0.1 to 1.0, and in these ranges, an effect of preparing an ester-based plasticizer composition having high process efficiency and an excellent processibility improving effect is obtained.
• composition ratio of the mixture of the three types of terephthalate-based materials is not limited to the above-mentioned ranges, and the composition ratios may be changed by additionally introducing any one of the three types of terephthalate, and mixing composition ratios that may be used are as described above.
• the trans-esterification may be conducted at a reaction temperature from 120° C. to 190° C., preferably from 135° C. to 180° C. and more preferably from 141° C. to 179° C. for 10 minutes to 10 hours, preferably from 30 minutes to 8 hours and more preferably from 1 hour to 6 hours.
• the mixture that is a terephthalate-based material having a target composition may be effectively obtained within the above-mentioned temperature and time ranges.
• the reaction time may be calculated from the time reaching a reaction temperature after raising the temperature of the reactants.
• the trans-esterification may be conducted under the presence of an acid catalyst or a metal catalyst, and in this case, an effect of shorter reaction time is obtained.
• the acid catalyst may comprise sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or the like
• the metal catalyst may comprise organic metal catalysts, metal oxide catalysts, metal salt catalysts or metals themselves.
• the metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more types of these.
• removing unreacted alcohol and reaction byproducts such as an ester-based compound represented by Chemical Formula 3 by distillation may be further included after the trans-esterification reaction.
• distillation may include two-step distillation carrying out separation of the alcohol and the reaction byproducts using a boiling point difference.
• the distillation may be mixed distillation.
• the mixed distillation means distilling the butanol and the reaction byproduct at the same time.
• the direct esterification and a trans-esterification may also be used in preparing the hybrid or non-hybrid acetyl citrate-based material or the trimellitate-based material.
• the acetyl citrate-based material may also be prepared as a mixed composition having a certain ratio, and a composition ratio of the produced mixture may be controlled depending on the adjustment of alcohol content as a reaction raw material.
• acetyl citrate-based material or the trimellitate-based material is prepared by a direct esterification or a trans-esterification
• descriptions used in preparing the terephthalate-based material may be used in the same manner.
• a resin composition may comprise 5 parts by weight to 150 parts by weight, 40 parts by weight to 100 parts by weight, or 40 parts by weight to 50 parts by weight of the plasticizer composition based on 100 parts by weight of a resin.
• the resin is selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomers.
• the resin composition is effective for all of compound formularization, sheet formularization and plastisol formularization.
• the plasticizer composition may be used in manufacturing wires, flooring materials, automotive interior materials, films, sheets, wallpapers or tubes.

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